M. Bortoluzzi et al. / Polyhedron 37 (2012) 66–76
69
3
3
3
3
7.61 (dd, 1H, JHH = 5.6 Hz, JHH = 7.7 Hz, pyridine-H5); 5.67 (d, 1H,
7.39 (dd, 1H, JHH = 5.4 Hz, JHH = 7.8 Hz, pyridine-H5); 5.49 (s, br,
2JHH = 13.0 Hz, CH2-O); 4.78 (d, 1H, JHH = 7.6 Hz, NH); 3.64 (m,
1H, CH2-O); 3.93 (d, 1H, JHH = 7.1 Hz, NH); 3.42 (s, br, 1H,
3
3
1H, CH-Namine); 2.86 (m, 1H, CH-Nimine); 2.50–1.00 (m, 20H, cyclo-
hexyl groups). 13C {1H} NMR (CD3NO2, 248 K): 155.3, 154.9 not H-
bonded carbon atoms; 154.0, 141.6, 128.3, 128.1 pyridine-CH; 72.0
CH-O; 54.0–25.0 cyclohexyl rings.
CH-Namine); 3.00 (s, br, 1H, CH-Nimine); 1.91 (s, 3H, CH3COO); 1.83
(s, 3H, CH3COO); 2.50–0.80 (m, 20H, cyclohexyl groups).
2.13. Characterization of 2Pr
2.10. Characterization of 1Pr
Elemental Anal. Calc. for C17H27N3O5Pd: C, 44.4; H, 5.92; N, 9.14.
Found: C, 44.5; H, 5.95; N, 9.15%. IR (KBr): 1625 cmꢀ1 (broad sig-
Elemental Anal. Calc. for C13H21Cl2N3OPd: C, 37.8; H, 5.13; Cl,
nal) mC@N and
mC@N and mC@O
m
.
C@O. IR (CH2Cl2): 1630 cmꢀ1 (shoulder), 1616 cmꢀ1
2
17.2; N, 10.2. Found: C, 37.8; H, 5.10; Cl, 17.1; N, 10.1%. IR (KBr):
1H NMR (CDCl3, 239 K): 9.58 (d, 1H, JHH = 13.0 Hz,
1613 cmꢀ1 mC@N
.
1H NMR (acetone-d6, 270 K): 8.80 (d, 1H,
CH2-O); 8.67 (d, 1H, JHH = 5.5 Hz, pyridine-H6); 7.87 (t, 1H,
3
3JHH = 5.5 Hz, pyridine-H6); 8.18 (t, 1H, JHH = 7.7 Hz, pyridine-H4);
3JHH = 7.6 Hz, pyridine-H4); 7.51 (d, 1H, JHH = 7.6 Hz, pyridine-H3);
3
3
2
3
3
3
8.07 (d, 1H, JHH = 12.7 Hz, CH2-O); 7.96 (d, 1H, JHH = 7.7 Hz, pyri-
7.41 (dd, 1H, JHH = 5.5 Hz, JHH = 7.6 Hz, pyridine-H5); 5.50 (d, 1H,
3
3
3
dine-H3); 7.74 (dd, 1H, JHH = 5.5 Hz, JHH = 7.7 Hz, pyridine-H5);
2JHH = 13.0 Hz, CH2-O); 4.12 (d, 1H, JHH = 6.6 Hz, NH); 3.77 (m,
2
3
5.83 (d, 1H, JHH = 12.7 Hz, CH2-O); 5.81 (d, 1H, JHH = 6.5 Hz, NH);
1H, CH-Namine); 2.87 (m, 1H, CH-Nimine); 1.89 (s, 3H, CH3COO);
3
3.99 (m, 1H, CH-Namine); 3.22 (sept, 1H, JHH = 6.4 Hz, CH-Nimine);
1.81 (s, 3H, CH3COO); 2.30–0.80 (m, 12H, (CH3)2CH). 1H NMR
3
3
3
1.81 (d, 3H, JHH = 6.4 Hz, (CH3)2CH-Nimine); 1.30 (d, 3H, JHH
=
(CDCl3, 317 K): 8.76 (d, 1H, JHH = 5.5 Hz, pyridine-H6); 7.83 (t, 1H,
6.4 Hz, (CH3)2CH-Nimine); 1.19 (d, 3H, 3JHH = 6.4 Hz, (CH3)2CH-Namine);
3JHH = 7.7 Hz, pyridine-H4); 7.48 (d, 1H, JHH = 7.7 Hz, pyridine-H3);
3
3
3
3
1.05 (d, 3H, JHH = 6.4 Hz, (CH3)2CH-Namine). 1H NMR (acetone-d6,
7.37 (dd, 1H, JHH = 5.5 Hz, JHH = 7.6 Hz, pyridine-H5); 4.00 (d, 1H,
3
3
318 K): 8.81 (d, 1H, JHH = 5.5 Hz, pyridine-H6); 8.13 (t, 1H,
3JHH = 6.9 Hz, NH); 3.81 (m, 1H, CH-Namine); 2.96 (sept, 1H, JHH
=
3JHH = 7.7 Hz, pyridine-H4); 7.88 (d, 1H, JHH = 7.7 Hz, pyridine-H3);
6.6 Hz, CH-Nimine); 1.89 (s, 3H, CH3COO); 1.81 (s, 3H, CH3COO);
3
3
3
3
3
7.69 (dd, 1H, JHH = 5.5 Hz, JHH = 7.7 Hz, pyridine-H5); 5.51 (d, 1H,
1.62 (d, br, 6H, JHH = 6.6 Hz, (CH3)2CH-Nimine); 1.05 (d, 6H, JHH
6.3 Hz, (CH3)2CH-Namine).
=
3JHH = 6.5 Hz, NH); 4.01 (m, 1H, CH-Namine); 3.28 (sept, 1H,
3JHH = 6.4 Hz, CH-Nimine); 1.57 (s, br, 6H, JHH = 6.4 Hz, (CH3)2CH-Ni-
3
mine); 1.16 (d, 6H, 3JHH = 6.4 Hz, (CH3)2CH-Namine). 1H NMR (CD3NO2,
2.14. Synthesis of Pd(CH3)Cl(pyiuCy) (3Cy) (C20H32ClN3OPd,
3
298 K): 8.74 (d, 1H, JHH = 5.7 Hz, pyridine-H6); 8.06 (t, 1H,
MW = 472.36 g molꢀ1) and Pd(CH3)Cl(pyiuPr) (3Pr) (C14H24ClN3OPd,
3JHH = 7.7 Hz, pyridine-H4); 8.01 (d, 1H, JHH = 12.9 Hz, CH2-O);
MW = 392.23 g molꢀ1
)
2
3
3
7.75 (d, 1H, JHH = 7.7 Hz, pyridine-H3); 7.63 (dd, 1H, JHH = 5.5 Hz,
3JHH = 7.7 Hz, pyridine-H5); 5.69 (d, 1H, JHH = 12.9 Hz, CH2-O);
To a solution of Pd(CH3)Cl(COD) (1.00 mmol, 0.265 g) in 20 mL
of CH2Cl2 a solution containing 1.00 mmol of freshly prepared
pyiuCy or pyiuPr in 10 mL of CH2Cl2 was slowly added. The result-
ing reaction mixture was left under stirring at room temperature
for 4 h, then the solvent was removed by evaporation under re-
duced pressure and diethylether (10 mL) was added. The solid
which separated out was filtered, washed with diethylether
(10 mL) and dried under vacuum. The products were purified by
slowly cooling saturated dichloromethane/diethylether solutions
from room temperature to ꢀ25 °C. Yield (3Cy) = 75%, 0.354 g. Yield
(3Pr) = 76%, 0.298 g.
2
3
4.78 (d, 1H, JHH = 7.5 Hz, NH); 3.97 (m, 1H, CH-Namine); 3.14 (sept,
3
3
1H, JHH = 6.4 Hz, CH-Nimine); 1.81 (d, 3H, JHH = 6.4 Hz, (CH3)2
3
CH-Nimine); 1.30 (d, 3H, JHH = 6.4 Hz, (CH3)2CH-Nimine); 1.19 (d,
3
3
3H, JHH = 6.4 Hz, (CH3)2CH-Namine); 1.05 (d, 3H, JHH = 6.4 Hz,
(CH3)2 CH-Namine). 13C {1H} NMR (CD3NO2, 298 K): 155.8, 155.5
not H-bonded carbon atoms; 154.2, 141.7, 128.3, 128.1 pyridine-
CH; 72.3 CH2-O; 53.4, 46.8 CH-N; 26.2, 23.7, 23.3, 22.6 (CH3)2CH-N.
2.11. Synthesis of Pd(OCOCH3)2(pyiuCy) (2Cy) (C23H35N3O5Pd,
MW = 539.96 g molꢀ1) and Pd(OCOCH3)2(pyiuPr) (2Pr
)
(C17H27N3O5Pd, MW = 459.83 g molꢀ1
)
2.15. Characterization of 3Cy
To a solution of palladium(II) acetate (1.00 mmol, 0.225 g) in
20 mL of CH2Cl2 a solution containing 1.00 mmol of freshly pre-
pared pyiuCy or pyiuPr in 10 mL of CH2Cl2 was slowly added. The
resulting reaction mixture was left under stirring at room temper-
ature for 4 h, then the solvent was removed by evaporation under
reduced pressure and diethylether (10 mL) was added. The solid
which separated out was filtered, washed with diethylether
(10 mL) and dried under vacuum. Yield (2Cy) = 90%, 0.486 g. Yield
(2Pr) = 88%, 0.407 g.
Elemental Anal. Calc. for C20H32ClN3OPd: C, 50.9; H, 6.83; Cl,
7.51; N, 8.90. Found: C, 50.8; H, 6.80; Cl, 7.50; N, 8.90%. IR (KBr):
1630 cmꢀ1 mC@N
.
1H NMR (CDCl3, 225 K): 8.54 (d, 1H, 3JHH = 5.5 Hz,
2
pyridine-H6); 8.02 (d, 1H, JHH = 12.5 Hz, CH2-O); 7.93 (t, 1H,
3JHH = 7.7 Hz, pyridine-H4); 7.62 (d, 1H, JHH = 7.7 Hz, pyridine-H3);
3
3
3
7.49 (dd, 1H, JHH = 5.5 Hz, JHH = 7.7 Hz, pyridine-H5); 5.32 (d, 1H,
2JHH = 12.5 Hz, CH2-O); 3.60 (d, 1H, JHH = 6.4 Hz, NH); 3.24 (m,
3
1H, CH-Namine); 2.57 (m, 1H, CH-Nimine); 2.30–0.90 (m, 20H, cyclo-
hexyl groups); 0.78 (s, 3H, Pd-CH3).
2.12. Characterization of 2Cy
2.16. Characterization of 3Pr
Elemental Anal. Calc. for C23H35N3O5Pd: C, 51.2; H, 6.53; N, 7.78.
Found: C, 51.3; H, 6.55; N, 7.80%. IR (KBr): 1610 cmꢀ1 (broad sig-
Elemental Anal. Calc. for C14H24ClN3OPd: C, 42.9; H, 6.17; Cl,
9.04; N, 10.7. Found: C, 43.0; H, 6.20; Cl, 9.05; N, 10.7%. IR (KBr):
nal) mC@N and
mC@N and mC@O
m
.
C@O. IR (CH2Cl2): 1630 cmꢀ1 (shoulder), 1609 cmꢀ1
2
1H NMR (CDCl3, 242 K): 9.64 (d, 1H, JHH = 13.4 Hz,
1629 cmꢀ1
m
C@N. 1H NMR (CD2Cl2, 241 K): 8.43 (d, 1H, 3JHH = 5.5 Hz,
3
3
CH2-O); 8.68 (d, 1H, JHH = 5.4 Hz, pyridine-H6); 7.87 (t, 1H,
pyridine-H6); 7.83 (t, 1H, JHH = 7.7 Hz, pyridine-H4); 7.81 (d, 1H,
3JHH = 7.8 Hz, pyridine-H4); 7.52 (d, 1H, JHH = 7.8 Hz, pyridine-H3);
2JHH = 12.0 Hz, CH2-O); 7.51 (d, 1H, JHH = 7.7 Hz, pyridine-H3);
3
3
3
3
3
3
7.40 (dd, 1H, JHH = 5.4 Hz, JHH = 7.8 Hz, pyridine-H5); 5.51 (d, 1H,
2JHH = 13.4 Hz, CH2-O); 4.03–3.15 (m, 3H, NH and CH-Namine and
CH-Nimine); 1.92 (s, 3H, CH3COO); 1.83 (s, 3H, CH3COO); 2.50–0.80
(m, 20H, cyclohexyl groups). 1H NMR (CDCl3, 271 K): 9.64 (s, br,
7.39 (dd, 1H, JHH = 5.5 Hz, JHH = 7.7 Hz, pyridine-H5); 5.25 (d, 1H,
2JHH = 12.0 Hz, CH2-O); 3.80–3.52 (m, 2H, NH and CH-Namine); 2.99
3
3
(sept, 1H, JHH = 6.4 Hz, CH-Nimine); 1.67 (d, 3H, JHH = 6.4 Hz,
3
(CH3)2CH-Nimine); 1.10 (d, 3H, JHH = 6.4 Hz, (CH3)2CH-Nimine); 1.02
3
3
3
1H, CH2-O); 8.71 (d, 1H, JHH = 5.4 Hz, pyridine-H6); 7.85 (t, 1H,
(d, 3H, JHH = 6.4 Hz, (CH3)2CH-Namine); 0.89 (d, 3H, JHH = 6.4 Hz,
(CH3)2CH-Namine); 0.57 (s, 3H, Pd-CH3).
3
3JHH = 7.8 Hz, pyridine-H4); 7.51 (d, 1H, JHH = 7.8 Hz, pyridine-H3);